WO2021149653A1 - 粘着剤組成物及び粘着シート - Google Patents

粘着剤組成物及び粘着シート Download PDF

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WO2021149653A1
WO2021149653A1 PCT/JP2021/001547 JP2021001547W WO2021149653A1 WO 2021149653 A1 WO2021149653 A1 WO 2021149653A1 JP 2021001547 W JP2021001547 W JP 2021001547W WO 2021149653 A1 WO2021149653 A1 WO 2021149653A1
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sensitive adhesive
pressure
adhesive composition
meth
active energy
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French (fr)
Japanese (ja)
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裕美 上野
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Oji Holdings Corp
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Oji Holdings Corp
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet.
  • a display device such as a liquid crystal display (LCD) and an input device used in combination with a display device such as a touch panel are widely used.
  • LCD liquid crystal display
  • an input device used in combination with a display device such as a touch panel
  • a transparent adhesive sheet is used for bonding optical members, and a transparent adhesive sheet is also used for bonding the display device and the input device.
  • Patent Document 1 is characterized by containing (A) a (meth) acrylic acid ester-based copolymer having a weight average molecular weight of 500,000 to 2.5 million, (B) a cross-linking agent, and (C) a radical scavenger.
  • the pressure-sensitive adhesive composition is disclosed.
  • Cited Document 1 it is studied to suppress the yellowing of the pressure-sensitive adhesive sheet formed from the pressure-sensitive adhesive composition by further containing (D) a secondary antioxidant.
  • Patent Document 2 discloses a photocurable resin containing a hydroxyphenyltriazine-based ultraviolet absorber and a hindered amine-based radical supplement as a photocurable resin to be impregnated in a glass fiber woven fabric.
  • the purpose of Patent Document 2 is to obtain a non-combustible sheet by impregnating a glass fiber woven fabric with a photocurable resin.
  • the pressure-sensitive adhesive composition When forming a photocurable pressure-sensitive adhesive sheet, the pressure-sensitive adhesive composition contains a photopolymerization initiator, and radicals are generated when the photopolymerization initiator is cleaved by light irradiation. While this radical promotes the polymerization of the monomer component contained in the pressure-sensitive adhesive composition, a part of the radical remains in the pressure-sensitive adhesive sheet and causes yellowing and deterioration of the pressure-sensitive adhesive sheet. Therefore, when forming a photocurable pressure-sensitive adhesive sheet, a radical scavenger may be added to capture radicals that cause yellowing or deterioration. However, it has been clarified by the studies by the present inventors that the yellowing may not be sufficiently suppressed even when a radical scavenger is added.
  • the present inventors have proceeded with studies for the purpose of forming an adhesive sheet having excellent yellowing resistance in the active energy ray-curable pressure-sensitive adhesive composition.
  • the present inventors have made a photopolymerization initiator having a predetermined structure by light irradiation in an active energy ray-curable pressure-sensitive adhesive composition containing an acrylic pressure-sensitive adhesive main agent.
  • a pressure-sensitive adhesive sheet having excellent yellowing resistance can be obtained by mixing a peroxide radical initiator and / or a hydroperoxide decomposing agent that does not generate quinone or stillbenquinone after capturing radicals. ..
  • the present invention has the following configuration.
  • Acrylic adhesive main agent and A photopolymerization initiator having the following structure (1) when irradiated with active energy rays,
  • An active energy ray-curable pressure-sensitive adhesive composition containing at least one selected from a peroxide radical scavenger and a hydroperoxide decomposing agent having no nitrogen atom.
  • the peroxide radical catching agent is an active energy ray-curable pressure-sensitive adhesive composition which is a radical catching agent that does not generate quinone or stillbenquinone after capturing the peroxide radical;
  • R 1 to R 5 independently represent a substituent containing a hydrogen atom, an alkyl group, a sulfur atom, a substituent containing a nitrogen atom, or a substituent containing an oxygen atom.
  • the photopolymerization initiator is at least one selected from the group consisting of an acetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator, according to [1].
  • Active energy ray-curable pressure-sensitive adhesive composition [3] The active energy ray-curable pressure-sensitive adhesive composition according to [1] or [2], wherein the peroxide radical supplement is a hindered phenol-based radical scavenger.
  • the (meth) acrylic polymer has a (meth) acrylic monomer unit having a hydroxyl group and has a hydroxyl group.
  • the adhesive sheet according to [9] which has a thickness of 100 ⁇ m or more.
  • an adhesive sheet having excellent yellowing resistance can be formed from an active energy ray-curable pressure-sensitive adhesive composition containing an acrylic pressure-sensitive adhesive main agent.
  • FIG. 1 is a schematic view showing a cross section of an adhesive sheet having a release sheet.
  • (meth) acrylic represents both acrylic and / or methacryl.
  • “monomer” and “monomer” are synonymous, and “polymer” and “polymer” are synonymous.
  • the present invention relates to an active energy ray-curable pressure-sensitive adhesive composition containing an acrylic pressure-sensitive adhesive main agent, a photopolymerization initiator, and at least one selected from a peroxide radical scavenger and a hydroperoxide decomposing agent. ..
  • the peroxide radical scavenger is a radical catching agent that does not produce quinone or stilbene quinone after capturing the peroxide radical.
  • the peroxide radical catching agent does not have a nitrogen atom.
  • the photopolymerization initiator is a photopolymerization initiator having the following structure (1) when irradiated with active energy rays.
  • the active energy ray-curable pressure-sensitive adhesive composition is also simply referred to as a pressure-sensitive adhesive composition.
  • R 1 to R 5 independently represent a substituent containing a hydrogen atom, an alkyl group, a sulfur atom, a substituent containing a nitrogen atom, or a substituent containing an oxygen atom.
  • the pressure-sensitive adhesive composition of the present invention contains a photopolymerization initiator, a peroxide radical scavenger and / or a hydroperoxide decomposing agent. Further, in the pressure-sensitive adhesive composition of the present invention, the polymerization of the acrylic pressure-sensitive adhesive main agent is started by the radical generated by the cleavage of the photopolymerization initiator.
  • the acid value of the pressure-sensitive adhesive composition of the present invention is preferably 1 mgKOH / g or less. This means that the pressure-sensitive adhesive composition of the present invention is substantially free of acid components. As described above, the pressure-sensitive adhesive composition of the present invention is preferably an acid-free pressure-sensitive adhesive composition. By setting the acid value of the pressure-sensitive adhesive composition within the above range, the yellowing resistance of the pressure-sensitive adhesive sheet is more effectively exhibited.
  • the active energy ray-curable pressure-sensitive adhesive composition of the present invention contains a photopolymerization initiator.
  • the photopolymerization initiator is cleaved so that at least a part thereof has the above structure (1).
  • R 1 to R 5 are independently substituents containing a hydrogen atom, an alkyl group, a substituent containing a sulfur atom, a substituent containing a nitrogen atom, or a substituent containing an oxygen atom.
  • the alkyl group may be a linear alkyl group or a branched alkyl group.
  • the alkyl group also includes a cycloalkyl group. Further, the alkyl group may be a group having a substituent further.
  • a substituent containing a sulfur atom a substituent containing a nitrogen atom or a substituent containing an oxygen atom
  • the sulfur atom, the nitrogen atom or the oxygen atom may be directly bonded to the benzene ring represented by the structure (1).
  • a sulfur atom, a nitrogen atom or an oxygen atom may form a heterocycle, and this heterocycle may be bonded to the benzene ring represented by the structure (1).
  • R 1 to R 5 independently represent a hydrogen atom or an alkyl group. Further, at least one of R 1 to R 5 is preferably a hydrogen atom, and more preferably two or more are hydrogen atoms. All of R 1 to R 5 may be hydrogen atoms.
  • the compound represented by the above structure (1) reacts with oxygen to become a peroxide radical.
  • the peroxide radical is represented by, for example, the following structure (2).
  • the peroxide radical reacts with hydrogen to form a hydroperoxide.
  • the hydroperoxide is represented by, for example, the following structure (2').
  • R 1 to R 5 independently represent a substituent containing a hydrogen atom, an alkyl group, a sulfur atom, a substituent containing a nitrogen atom, or a substituent containing an oxygen atom. ..
  • the preferred embodiments of R 1 to R 5 in the structures (2) and (2') are the same as the preferred embodiments of R 1 to R 5 in the structure (1).
  • the peroxide radicals represented by the above structure (2) react with the peroxide radical scavenger described later to capture the radicals in the pressure-sensitive adhesive sheet, thereby suppressing yellowing and deterioration of the pressure-sensitive adhesive sheet. Will be done. Further, in the present invention, when the peroxide radical reacts with the peroxide radical scavenger described later, quinone or stilbene quinone is not generated, so that the yellowing resistance of the pressure-sensitive adhesive sheet is effectively suppressed. .. Further, the hydroperoxide as represented by the above structure (2') is decomposed to generate radicals.
  • the reaction between the hydroperoxide and the hydroperoxide decomposing agent results in a structure that does not generate radicals, which suppresses yellowing and deterioration of the pressure-sensitive adhesive sheet.
  • sulfur-based and phosphorus-based hydroperoxide decomposing agents do not color after the reaction, the yellowing resistance effect of the pressure-sensitive adhesive sheet is more effectively exhibited.
  • Examples of the photopolymerization initiator having the above structure (1) by irradiation with active energy rays include a photopolymerization initiator having the following structure (3).
  • the photopolymerization initiator having the above structure (1) by irradiation with active energy rays is at least selected from the group consisting of an acetophenone-based photopolymerization initiator, an acylphosphine oxide-based photopolymerization initiator, and an oxime ester-based photopolymerization initiator. It is preferably one kind.
  • R 1 to R 5 independently represent a substituent containing a hydrogen atom, an alkyl group, a sulfur atom, a substituent containing a nitrogen atom, or a substituent containing an oxygen atom.
  • the preferred embodiments of R 1 to R 5 in the structure (3) are the same as the preferred embodiments in the structure (1).
  • X is a substituent.
  • the photopolymerization initiator having the structure (3) include benzoin, benzoine ether, benzylmethyl ketal, ⁇ -hydroxyketone, ⁇ -aminoketone, acylphosphine oxide, and oxime ester.
  • a commercially available product can also be used as the photopolymerization initiator that has the above structure (1) when irradiated with active energy rays.
  • the content of the photopolymerization initiator is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and 0.1 part by mass or more with respect to 100 parts by mass of the pressure-sensitive adhesive main agent. It is more preferable to have.
  • the content of the photopolymerization initiator is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and further preferably 3 parts by mass or less with respect to 100 parts by mass of the pressure-sensitive adhesive main agent. preferable.
  • the polymerization curing reaction can be effectively carried out, and the molecular weight of the acrylic pressure-sensitive adhesive base after polymerization can be set within a preferable range, so that the adhesive strength of the pressure-sensitive adhesive sheet can be increased. Can be enhanced.
  • the active energy ray-curable pressure-sensitive adhesive composition of the present invention contains at least one selected from a peroxide radical scavenger and a hydroperoxide decomposing agent having no nitrogen atom.
  • the peroxide radical trapping agent and the hydroperoxide decomposing agent may be used alone, in which case the active energy ray-curable pressure-sensitive adhesive composition is a peroxide radical trapping agent or hydro without a nitrogen atom.
  • a peroxide radical scavenger having no nitrogen atom and a hydroperoxide decomposing agent may be used in combination.
  • the peroxide radical scavenger is a radical catching agent that captures the peroxide radical derived from the above-mentioned photopolymerization initiator.
  • the above-mentioned photopolymerization initiator is cleaved to become the above-mentioned structure (1), and the compound represented by the above-mentioned structure (1) is reacted with oxygen to become a peroxide radical.
  • the peroxide radical scavenger captures this peroxide radical.
  • the peroxide radical scavenger used in the present invention does not have a nitrogen atom and has a structure that does not generate quinone or stilbene quinone when the peroxide radical is supplemented. Therefore, the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition of the present invention has excellent yellowing resistance.
  • a peroxide radical scavenger having no nitrogen atom has a high radical scavenging ability against oxidative deterioration due to heat, and is difficult to color because it does not have a nitrogen atom in its structure. Further, in the peroxide radical scavenger having no nitrogen atom, even if the addition amount is large, it does not bleed out from the pressure-sensitive adhesive sheet, and it is possible to suppress unevenness and contamination of the adherend. Will be done.
  • the peroxide radical scavenger used in the present invention preferably has a ring structure, and one ring structure preferably does not have two or more ketone groups.
  • the ring structure of the peroxide radical scavenger has a hydroxyl group, it is preferable that a long chain or a bulky substituent is bonded to the hydroxyl group at the para position.
  • the peroxide radical scavenger having a structure that does not generate quinone or stillbenquinone when the peroxide radical is supplemented include a hindered phenol-based radical scavenger.
  • the peroxide radical scavenger is preferably a compound having a substituent having a molecular weight of 200 or more at the para position with respect to the hydroxyl group of the hindered phenol in the hindered phenol-based radical scavenger.
  • examples of the substituent having a molecular weight of 200 or more include an alkyl group which may have a substituent
  • examples of the substituent having an alkyl group include a group having a heterocyclic structure and an aromatic ring structure.
  • the substituent contained in the alkyl group may further contain a hindered phenol structure.
  • the above-mentioned hindered phenolic radical scavenger as the peroxide radical scavenger, yellowing of the pressure-sensitive adhesive sheet can be prevented and a decrease in adhesive strength can be further suppressed by adding a small amount.
  • hindered phenolic radical trapping agent examples include octadecyl 3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetrakis (3- (3,5-di-t-butyl-4).
  • a commercially available product can also be used as a peroxide radical scavenger that does not have a nitrogen atom and has a structure that does not generate quinone or stilbene quinone when the peroxide radical is supplemented.
  • Examples of commercially available products include a hindered phenol-based peroxide radical scavenger, Sumitomo Chemical's Sumilyzer GA80, ADEKA's ADEKA STAB AO-50, AO-60, AO-330, and BASF's Irganox 245.
  • a hydroperoxide decomposing agent is a compound having a structure that does not generate radicals by reacting with a hydroperoxide, and is also called a secondary antioxidant.
  • a sulfur-based hydroperoxide decomposing agent and a phosphorus-based hydroperoxide decomposing agent can be preferably exemplified.
  • the sulfur-based hydroperoxide decomposing agent is a hydroperoxide decomposing agent having at least one sulfur atom
  • the phosphorus-based hydroperoxide decomposing agent is a hydroperoxide decomposing agent having at least one phosphorus atom.
  • the sulfur-based hydroperoxide decomposing agent is preferably a compound having a thioether group.
  • the number of carbon atoms of the terminal alkyl group linked to the compound having a thioether group is preferably 15 or less, and more preferably 12 or less.
  • sulfur-based hydroperoxide decomposing agent examples include distearyl 3,3'-thiodi-propionate, dislauryl 3,3'-thiodi-propionate, and 2,2-bis ( ⁇ [3- (dodecylthio) propionyl] oxy ⁇ .
  • Methyl) -1,3-propanediyl-bis [3- (dodecylthio) propionate] and the like can be mentioned.
  • the phosphorus-based hydroperoxide decomposing agent is preferably a phosphite-based antioxidant.
  • phosphite-based antioxidants the larger the steric hindrance around the phosphorus atom, the less likely it is to be hydrolyzed, and the more effectively it reacts with hydroperoxide.
  • the phosphorus-based hydroperoxide decomposing agent may be a compound having an aromatic ring structure, and the aromatic ring may further have a substituent.
  • Examples of the substituent having an aromatic ring include an alkyl group such as a t-butyl group, and a phosphorus-based hydroperoxide decomposing agent having an aromatic ring to which at least two or more t-butyl groups are added can be preferably exemplified. ..
  • a hydroperoxide decomposing agent having an aromatic ring to which at least two t-butyl groups are added as a phosphorus-based hydroperoxide decomposing agent, hydrolysis is suppressed, and a small amount of addition causes yellowing of the pressure-sensitive adhesive. Can be prevented and the decrease in adhesive strength can be suppressed.
  • Examples of the phosphorus-based hydroperoxide degrading agent include 6- [3- (3-t-butyl-4-hydroxy-5-methyl) propoxy] -2,4,8,10-tetra-t-butyldibenz [d]. , F] [1,3,2] -dioxaphosphine, 3,9-bis (2,6-di-t-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9 -Diphosphaspiro [5,5] undecane, 2,4,8,10-tetra-t-butyl-6-[(2-ethylhexane-1-yl) oxy] -12H-dibenzo [d, g] [1, 3,2] Dioxaphosphosin, tris (2,4-di-t-butylphenyl) phosphite and the like can be mentioned.
  • a commercially available product can be used as a hydroperoxide decomposing agent that does not produce quinone or stilbene quinone after decomposing hydroperoxide.
  • sulfur-based hydroperoxide decomposing agent include Sumitomo Chemical's Sumilyzers TP-D and TP-L, ADEKA's ADEKA STAB AO-412S, and AO-503.
  • phosphorus-based hydroperoxide decomposing agent include Sumitomo Chemical's Sumilyzer GP, Adecaster PEP-8, PEP-36, HP-10, 2112 and the like.
  • the content of the peroxide radical scavenger is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, and 0.075 part by mass with respect to 100 parts by mass of the pressure-sensitive adhesive main agent.
  • the above is more preferable.
  • the content of the peroxide radical scavenger is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and 3 parts by mass or less with respect to 100 parts by mass of the pressure-sensitive adhesive main agent. Is more preferable, and it is more preferably 2 parts by mass or less, and particularly preferably 1 part by mass or less.
  • the pressure-sensitive adhesive composition of the present invention has an acrylic pressure-sensitive adhesive main agent.
  • the pressure-sensitive adhesive main agent is a main component that is polymerized by the above-mentioned photopolymerization initiator to form a pressure-sensitive adhesive sheet.
  • the acrylic pressure-sensitive adhesive base material preferably contains a (meth) acrylic polymer.
  • the acrylic pressure-sensitive adhesive main agent preferably contains a monomer constituting the (meth) acrylic polymer in addition to the (meth) acrylic polymer.
  • the acrylic pressure-sensitive adhesive main agent is preferably an acrylic syrup. The monomer component contained in the acrylic syrup is polymerized in the process of producing the pressure-sensitive adhesive sheet to form a (meth) acrylic polymer.
  • the (meth) acrylic polymer preferably contains a (meth) acrylic monomer unit having a hydroxyl group.
  • examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 3-chloro-2-hydroxy.
  • examples thereof include propyl (meth) acrylate, 4-hydroshikibutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, and polyalkylene glycol mono (meth) acrylate.
  • at least one selected from 2-hydroxyethyl (meth) acrylate and 4-hydroshikibutyl (meth) acrylate is preferably used.
  • the content of the (meth) acrylic monomer unit having a hydroxyl group in the (meth) acrylic polymer is preferably 20% by mass or more, preferably 25% by mass or more, based on the total mass of the (meth) acrylic polymer. Is even more preferable. Further, the content of the (meth) acrylic monomer unit having a hydroxyl group in the (meth) acrylic polymer is preferably 50% by mass or less with respect to the total mass of the (meth) acrylic polymer.
  • the (meth) acrylic polymer may contain an alkyl (meth) acrylate unit in addition to the (meth) acrylic monomer unit having a hydroxyl group.
  • alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, and decyl (meth).
  • alkyl (meth) acrylates such as meth) acrylates, lauryl (meth) acrylates, cetyl (meth) acrylates, stearyl (meth) acrylates, and behenyl (meth) acrylates.
  • the (meth) acrylic polymer may have a (meth) acrylic monomer unit having a crosslinkable functional group in addition to the (meth) acrylic monomer unit having a hydroxyl group.
  • the crosslinkable functional group contained in the (meth) acrylic monomer having a crosslinkable functional group include an amide group, an amino group, a thiol group, an isocyanate group, an epoxy group and a silanol group.
  • the content of the (meth) acrylic monomer unit having a crosslinkable functional group in the (meth) acrylic polymer is preferably 10% by mass or less, and more preferably 5% by mass or less.
  • the (meth) acrylic polymer has substantially no carboxy group.
  • the content of the (meth) acrylic monomer unit having a carboxy group in the (meth) acrylic polymer is preferably 1% by mass or less, preferably 0.1% by mass, based on the total mass of the (meth) acrylic polymer. The following is more preferable.
  • the (meth) acrylic polymer may have other monomer units, if necessary.
  • the other monomer may be a monomer copolymerizable with the above-mentioned monomer component, and examples thereof include (meth) acrylonitrile, vinyl acetate, vinyl chloride, and ethyl vinyl ether.
  • the content of the other monomer unit in the (meth) acrylic polymer is preferably 10% by mass or less, and more preferably 5% by mass or less.
  • the pressure-sensitive adhesive composition of the present invention may contain a polyfunctional monomer having two or more reactive double bonds in the molecule.
  • the polyfunctional monomer has two or more reactive double bonds, and among them, the polyfunctional monomer preferably has two or more and less than five reactive double bonds, and two or more and less than four. It is more preferable to have.
  • polyfunctional monomer examples include polyethylene glycol diacrylate, polypropylene diacrylate, alkyl diacrylate, polytetramethylene glycol diacrylate, polypropylene glycol diacrylate, dioxane diacrylate, tricyclodecanol diacrylate, and full as bifunctional monomer.
  • Orange acrylate can be mentioned.
  • alkoxylated trimethylolpropane triacrylate alkoxylated glycerin triacrylate, caprolactone-modified isocyanurate triacrylate, pentaerythritol acrylate, alkoxylated pentaeryllitol acrylate, (alkoxylated) pentaerythritol acrylate, Examples thereof include (alkoxylated) ditrimethylolpropane acrylate, (alkoxylated) dipentaerythritol acrylate, and (ethoxylated) polyglycerin acrylate.
  • the polyfunctional monomer is preferably a polyfunctional monomer having an alkylene glycol group in one molecule.
  • the number of alkylene glycol groups in one molecule is preferably 1 to 20.
  • Examples of such a polyfunctional monomer include polyethylene glycol diacrylate and trimethylolpropane propylene oxide-modified triacrylate.
  • a commercially available product can be used as the polyfunctional monomer.
  • Examples of commercially available products are manufactured by Shin-Nakamura Chemical Industry Co., Ltd., bifunctional monomer A-200 (polyethylene glycol # 200 diacrylate), trifunctional monomer A-TMPT ((alkoxylated) trimethylolpropane acrylate), manufactured by Toa Synthetic Co., Ltd.
  • Examples thereof include a bifunctional monomer M240 (polyethylene glycol diacrylate) and a tetrafunctional monomer M-408 (ditrimethylolpropane tetraacrylate).
  • the polyfunctional monomer forms a crosslinked structure with the above-mentioned (meth) acrylic polymer in the pressure-sensitive adhesive sheet.
  • the content of the polyfunctional monomer in the pressure-sensitive adhesive composition is preferably 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total mass of the pressure-sensitive adhesive composition. More preferred. By setting the content of the polyfunctional monomer within the above range, the hardness of the pressure-sensitive adhesive sheet can be increased, and the durability and processability of the pressure-sensitive adhesive sheet can be improved.
  • the pressure-sensitive adhesive composition may contain a cross-linking agent.
  • the cross-linking agent can be appropriately selected in consideration of the reactivity of the (meth) acrylic polymer with the cross-linking functional group.
  • it can be selected from known cross-linking agents such as isocyanate compounds, epoxy compounds, oxazoline compounds, aziridine compounds, metal chelate compounds, and butylated melamine compounds.
  • the cross-linking agent preferably contains at least one selected from an isocyanate compound, an epoxy compound and a metal chelate compound.
  • Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like.
  • Examples of commercially available products include tolylene diisocyanate compounds (manufactured by Tosoh Corporation, Coronate L), xylylene diisocyanate compounds (manufactured by Mitsui Chemicals, Inc., Takenate D-110N) and the like.
  • Examples of the epoxy compound include TETRAD-C (manufactured by Mitsubishi Gas Chemical Company) and TETRAD-X (manufactured by Mitsubishi Gas Chemical Company).
  • Examples of the metal chelate compound include aluminum chelate A (manufactured by Kawaken Fine Chemicals).
  • the cross-linking agent constitutes a cross-linked structure with the above-mentioned (meth) acrylic polymer in the pressure-sensitive adhesive sheet. However, some of the cross-linking agents are detected without forming a cross-linked structure.
  • the content of the cross-linking agent in the pressure-sensitive adhesive composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total mass of the pressure-sensitive adhesive composition. preferable. By setting the content of the cross-linking agent within the above range, the hardness of the pressure-sensitive adhesive sheet can be increased, and the durability and processability of the pressure-sensitive adhesive sheet can be improved.
  • silane coupling agent examples include a mercapto-based silane coupling agent containing a mercapto group, an epoxy-based silane coupling agent having an epoxy group, a vinyl-based silane coupling agent having a vinyl group, and the like.
  • the content of the silane coupling agent in the pressure-sensitive adhesive composition is preferably 0.1 part by mass or more, and more preferably 0.3 part by mass or more with respect to 100 parts by mass of the (meth) acrylic polymer. , 0.5 parts by mass or more, and particularly preferably 0.8 parts by mass or more.
  • the content of the silane coupling agent in the pressure-sensitive adhesive composition is preferably 10 parts by mass or less with respect to 100 parts by mass of the (meth) acrylic polymer.
  • the pressure-sensitive adhesive composition may contain other components other than the above as long as the effects of the present invention are not impaired.
  • other components include components known as additives for adhesives.
  • a plasticizer, an acid scavenger, a metal corrosion inhibitor, an ultraviolet absorber, or the like can be selected as needed.
  • dyes and pigments may be added for the purpose of coloring.
  • a non-functional group acrylic polymer may be used.
  • the non-functional group acrylic polymer a polymer consisting only of an acrylic monomer unit having no functional group other than an acrylate group, or an acrylic monomer unit having no functional group other than an acrylate group and having no functional group.
  • a polymer composed of a non-acrylic monomer unit can be mentioned. Since the non-functional group acrylic polymer is not crosslinked, it is possible to improve the step followability when the non-functional group acrylic polymer is attached to the adherend without affecting the adhesiveness.
  • the acid scavenger include carbodiimide-based acid scavengers.
  • a benzotriazole-based resin can be mentioned as a preferable example because of the compatibility and high effect of the pressure-sensitive adhesive.
  • the ultraviolet absorber include benzotriazole-based compounds, benzophenone-based compounds, and triazine-based compounds.
  • the present invention also relates to a pressure-sensitive adhesive sheet obtained by curing the above-mentioned pressure-sensitive adhesive composition (coating liquid).
  • the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet composed of only a pressure-sensitive adhesive layer, and preferably a double-sided pressure-sensitive adhesive sheet.
  • the double-sided adhesive sheet includes a single-layer adhesive sheet composed of an adhesive layer, a multi-layer adhesive sheet in which a plurality of adhesive layers are laminated, and a multi-layer adhesive in which another adhesive layer is laminated between the adhesive layers.
  • the sheet can be mentioned.
  • the pressure-sensitive adhesive sheet of the present invention may be a multi-layered pressure-sensitive adhesive sheet in which a support is laminated between the pressure-sensitive adhesive layer and the pressure-sensitive adhesive layer. When the double-sided adhesive sheet has a support, it is preferable to use a transparent support as the support.
  • a general film used in the optical field can be used as in the case of the transparent substrate. Since such a double-sided pressure-sensitive adhesive sheet is also excellent in transparency of the pressure-sensitive adhesive sheet as a whole, it can be suitably used for bonding optical members to each other.
  • the present invention may relate to an adhesive sheet with a release sheet having release sheets on both surfaces of the adhesive sheet.
  • the pressure-sensitive adhesive sheet 10 with the release sheet may have the release sheets 12a and 12b on both surfaces of the pressure-sensitive adhesive layer 11 as shown in FIG. preferable.
  • the release sheet is a removable laminated sheet having a release sheet base material and a release agent layer provided on one side of the release sheet base material, or a polyolefin film such as a polyethylene film or polypropylene film as a low-polarity base material. Can be mentioned. Papers and polymer films are used as the base material for the release sheet in the releaseable laminated sheet.
  • a general-purpose addition-type or condensation-type silicone-based release agent or a long-chain alkyl group-containing compound is used.
  • an addition type silicone release agent having high reactivity is preferably used.
  • a commercially available product may be used as the peelable laminated sheet.
  • Examples thereof include the heavy separator film A71, which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd., and the light separator film A38ST, which is a release-treated polyethylene terephthalate film manufactured by Teijin DuPont Film Co., Ltd. be able to.
  • the pressure-sensitive adhesive sheet with a release sheet preferably has a pair of release sheets having different peeling forces on both surfaces of the pressure-sensitive adhesive sheet. That is, it is preferable that the release sheet has different peelability between the release sheet 12a and the release sheet 12b in order to facilitate the release. When the peelability from one side and the peelability from the other side are different, it becomes easy to peel off only the release sheet having the higher peelability first. In that case, the peelability of the release sheet 12a and the release sheet 12b may be adjusted according to the bonding method and the bonding order.
  • the thickness of the pressure-sensitive adhesive sheet can be appropriately set according to the intended use, and is not particularly limited, but is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, further preferably 50 ⁇ m or more, and further preferably 75 ⁇ m or more. Is more preferable, and 100 ⁇ m or more is particularly preferable.
  • the thickness of the pressure-sensitive adhesive sheet is preferably 5000 ⁇ m or less, more preferably 3000 ⁇ m or less, and even more preferably 1000 ⁇ m or less. Normally, the thicker the pressure-sensitive adhesive sheet, the more remarkable the yellowing becomes. However, since the pressure-sensitive adhesive sheet of the present invention has excellent yellowing resistance, even if the thickness of the pressure-sensitive adhesive sheet is thick, the yellowness becomes remarkable. Is kept low.
  • the method for producing an adhesive sheet of the present invention preferably includes a step of applying an adhesive composition on a release sheet to form a coating film and a step of irradiating the coating film with active energy rays.
  • the coating of the pressure-sensitive adhesive composition can be carried out using a known coating device.
  • the coating device include a blade coater, an air knife coater, a roll coater, a bar coater, a gravure coater, a micro gravure coater, a rod blade coater, a lip coater, a die coater, a curtain coater and the like.
  • the integrated light amount is irradiated with active energy rays so that 100 ⁇ 10000mJ / cm 2, an active energy ray such that 500 ⁇ 5000mJ / cm 2 It is more preferable to do so.
  • the active energy ray may be irradiated in two steps. For example, the irradiation intensity of the second stage can be increased as compared with the first stage.
  • the pressure-sensitive adhesive sheet of the present invention is preferably used for bonding optical members.
  • the optical member include each component in an optical product such as a touch panel and an image display device.
  • the constituent members of the touch panel include an ITO film in which an ITO film is provided on a transparent resin film, an ITO glass in which an ITO film is provided on the surface of a glass plate, and a transparent conductive film in which a transparent resin film is coated with a conductive polymer.
  • Examples include hard coat films and fingerprint resistant films.
  • the constituent members of the image display device include an antireflection film, an alignment film, a polarizing film, a retardation film, and a brightness improving film used in a liquid crystal display device.
  • the adhesive sheet of the present invention may be used for bonding modules such as a liquid crystal module and a touch panel module to each other.
  • modules such as a liquid crystal module and a touch panel module
  • the material used for these members include glass, polycarbonate, polyethylene terephthalate, polymethylmethacrylate, polyethylene naphthalate, cycloolefin polymer, triacetyl cellulose, polyimide, and cellulose acylate.
  • Example 1 (Preparation of syrup containing (meth) acrylic polymer) Put 620 g of butyl acrylate, 220 g of 4-hydroxyl butyl acrylate, 70 g of 2-hydroxyethyl methacrylate, 90 g of cyclohexyl methacrylate, and 0.2 g of n-dodecyl mercaptan into a 2 L flask equipped with a stirrer, nitrogen introduction tube, cooling tube, and thermometer. Then, after nitrogen substitution at a nitrogen flow rate of 300 ml / min for 60 minutes, the nitrogen flow rate was lowered to 100 ml / min, and the temperature was raised to 60 ° C. in a water bath for heating.
  • the coating liquid is applied onto a 50 ⁇ m polyester film coated with a silicone release agent so that the thickness of the pressure-sensitive adhesive layer is 175 ⁇ m, and a 50 ⁇ m polyester film coated with a silicone release agent is further layered on top of the coating liquid. rice field. Then, the pressure-sensitive adhesive sheet of Example 1 was obtained by irradiating with a chemical lamp at a light intensity of 7 mW / cm 2 for 2 minutes and then irradiating with a high-pressure mercury lamp so that the integrated light intensity was 1500 mJ / cm 2.
  • Example 2 The monomer composition in (Preparation of syrup containing (meth) acrylic polymer) was changed as shown in Table 1, and in (Preparation of adhesive sheet), IGM RESINS B.I. An adhesive sheet was obtained in the same manner as in Example 1 except that 0.3 g of Omnirad 184 manufactured by V was used.
  • Example 3 In (Preparation of Adhesive Sheet), IGM RESINS B.I. An adhesive sheet was obtained in the same manner as in Example 1 except that 0.1 g of Omnirad 819 manufactured by V was used.
  • Example 4 In (Preparation of Adhesive Sheet), the adhesive sheet was used in the same manner as in Example 1 except that 0.2 g of ADEKA ADEKA STAB AO-50 was used as a hindered phenolic peroxide radical scavenger and the thickness of the adhesive sheet was 150 ⁇ m.
  • Example 5 In (Preparation of Adhesive Sheet), the same as in Example 1 except that 0.1 g of TP-D manufactured by Sumitomo Chemical Co., Ltd. was used as a hydroperoxide decomposing agent instead of the peroxide radical scavenger and the thickness of the adhesive sheet was set to 150 ⁇ m. And obtained an adhesive sheet.
  • Example 6 In (Preparation of Adhesive Sheet), an adhesive sheet was obtained in the same manner as in Example 1 except that 0.1 g of ADEKA's ADEKA STUB 2112 was used as a hydroperoxide decomposing agent instead of the peroxide radical scavenger.
  • Example 7 A pressure-sensitive adhesive composition and a pressure-sensitive adhesive sheet were obtained in the same manner as in Example 1 except that the monomer composition in (Preparation of syrup containing (meth) acrylic polymer) was changed as shown in Table 1.
  • Example 8 In (Preparation of Adhesive Sheet), the adhesive sheet was prepared in the same manner as in Example 5 except that 0.2 g of Sumilyzer GA80, which is a hindered phenol-based peroxide radical scavenger, was further added in addition to the hydroperoxide decomposing agent. Obtained.
  • Sumilyzer GA80 which is a hindered phenol-based peroxide radical scavenger
  • GA80 Sumilyzer GA80 (hindered phenolic peroxide radical scavenger)
  • Adecastab AO-50 hindered phenolic peroxide radical scavenger
  • TP-D Sumilyzer TP-D (sulfur-based hydroperoxide decomposing agent; (H 25 C 12 SCH 2 CH 2 COOCH 2 ) 4 C 2112: Adecastab 2112 (phosphorus hydroperoxide decomposing agent)
  • MEHQ Methoxyhydroquinone (phenolic peroxide radical scavenger)
  • BHT Dibutylhydroxytoluene (phenolic peroxide radical scavenger)
  • 770DF Tinuvin 770DF bis (2,2,6,6-tetramethylpiperidine-4-yl) -decandioart (hindered amine stabilizer)
  • the peroxide radical compensator did not produce quinone and stillbenquinone after capturing the peroxide radical, while in the pressure-sensitive adhesive sheet of Comparative Example, the peroxide radical-capturing agent. Produces quinones and stillbenquinones. Therefore, the laminated body to which the adhesive sheets obtained in the examples were bonded was excellent in yellowing resistance.

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JP2011168688A (ja) * 2010-02-18 2011-09-01 Maxell Sliontec Ltd 光学用粘着テープまたはシートおよびその製造方法
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JP2011168688A (ja) * 2010-02-18 2011-09-01 Maxell Sliontec Ltd 光学用粘着テープまたはシートおよびその製造方法
CN103450818A (zh) * 2012-06-05 2013-12-18 祐鼎（福建）光电材料有限公司 使用透明压克力单体的光学胶
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